An epoxy resin composite material and a method for producing the same

Abstract

This invention discloses an epoxy resin composite material and its preparation method. The composite material is prepared from the following components in parts by weight: 250-600 parts curing agent, 500-800 parts epoxy resin, 1-30 parts accelerator, and 20-130 parts fluorinated graphene. A method for preparing the epoxy resin composite material involves uniformly mixing 250-600 parts curing agent, 500-800 parts epoxy resin, 1-30 parts accelerator, and 20-130 parts fluorinated graphene, adding the mixture to a mold, and setting an electric field around the mold with an electric field strength of 5-10 kV / m. The mixture is cured at 70-80℃ for 1-3 hours, or at 150-190℃ for 1-12 hours, and then the mold is opened to obtain the product. In this invention, fluorinated graphene can significantly improve the mechanical properties and barrier properties of the composite material, greatly expanding the application of epoxy resin composite materials in the high-barrier field.

Description

Technical Field

[0001] This invention belongs to the field of polymer material modification technology, specifically relating to an epoxy resin composite material and its preparation method. Background Technology

[0002] Thermosetting resins are polymers that are cured into a rigid shape using thermosetting or radiation methods. The curing process is irreversible because it introduces a polymer network cross-linked by covalent bonds. Unlike thermoplastics, thermosetting plastics remain solid when heated until they begin to degrade at the desired temperature. Epoxy resin is a typical thermosetting resin with the molecular formula (C11H12O3)n, referring to a class of polymers containing two or more epoxy groups in their molecules. It is a condensation product of epichlorohydrin and bisphenol A or a polyol. The molecular structure of epoxy resins is characterized by the presence of reactive epoxy groups in the molecular chain; these epoxy groups can be located at the ends, in the middle, or in a cyclic structure. Due to the presence of reactive epoxy groups in their molecular structure, they can undergo cross-linking reactions with various types of curing agents to form insoluble, infusible polymers with a three-dimensional network structure.

[0003] Epoxy resin possesses excellent physical, mechanical, and electrical insulation properties, strong adhesion to various materials, and flexible processing capabilities unmatched by other thermosetting plastics. Therefore, it can be used to manufacture coatings, composite materials, castings, adhesives, molding materials, and injection molding materials, finding wide application in various sectors of the national economy. However, when epoxy resin is directly used to manufacture fuel tanks and fuel lines, its barrier properties fail to meet the required standards. Summary of the Invention

[0004] The purpose of this invention is to provide an epoxy resin composite material and its preparation method, so as to solve the problem that the barrier properties of existing epoxy resin composite materials cannot meet the requirements of high barrier applications.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] An epoxy resin composite material, characterized in that it is prepared from the following components in parts by weight:

[0007]

[0008] The epoxy resin is selected from at least one of glycidyl epoxy resins and non-glycidyl epoxy resins.

[0009] Furthermore, the epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, linear phenolic epoxy resin, aliphatic glycidyl ether resin, tetrabromobisphenol A epoxy resin, and alicyclic epoxy resin.

[0010] The curing agent is selected from at least one of amine curing agents, acid anhydride curing agents, synthetic resin curing agents, and polysulfide rubber curing agents.

[0011] Furthermore, the amine curing agent is selected from at least one of polyamine curing agents, tertiary amine and imidazole curing agents, boramine and its boramine complex curing agents.

[0012] Preferably, the curing agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, m-phenylenediamine, bis(4-amino-3-methylcyclohexyl)methane, isophorone diamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, triethanolamine, and N,N′-dimethylpiperazine.

[0013] Preferably, the curing agent is selected from at least one of pyromellitic anhydride, benzophenone tetracarboxylic anhydride, phthalic anhydride, methyltetrahydroanhydride, methylnadic anhydride, and dodecyl succinic anhydride.

[0014] The accelerator is at least one of benzyldimethylamine, 2-methylimidazole, triethanolamine, and benzylimidazole.

[0015] The fluorinated graphene has a fluorine-to-carbon ratio of ≥1.0, a bulk density of ≥0.02 g / cm³, and a particle size D50 of 1-20 μm.

[0016] A method for preparing an epoxy resin composite material, characterized by: uniformly mixing 250-600 parts of curing agent, 500-800 parts of epoxy resin, 1-30 parts of accelerator, and 20-130 parts of fluorinated graphene, adding the mixture to a mold, and setting an electric field around the mold with an electric field strength of 5-10 kV / m. Curing is performed at 70-80℃ for 1-3 hours, or at 150-190℃ for 1-12 hours, and then the mold is opened to obtain the product.

[0017] Beneficial effects:

[0018] (1) The mechanism of anhydride curing of epoxy resin involves etherification and esterification reactions, as well as a certain catalytic effect, making the reaction mechanism very complex. Methyltetrahydrophthalic anhydride, also known as methyltetrahydrophthalic anhydride, has the advantages of fast curing speed and good thermal stability in this invention. 2-Methylimidazole is both an accelerator and a curing agent. In this invention, it works synergistically with methyltetrahydrophthalic anhydride to achieve better and more uniform dispersion of fluorinated graphene. Methyltetrahydrophthalic anhydride itself is not very reactive, and there are no delocalized π bonds in its molecule. In addition, due to the steric hindrance of the methyl group, its nucleophilic effect is weak. However, in this invention, when methyltetrahydrophthalic anhydride and the accelerator are present, it can maximize the expansion of fluorinated graphene from a coiled shape to a two-dimensional planar shape in the plane. It can be uniformly dispersed in the composite material by lamination, thereby significantly improving the mechanical properties and barrier properties of the composite material.

[0019] (2) In this invention, fluorinated graphene can significantly improve the mechanical properties and barrier properties of composite materials, greatly expanding the application of epoxy resin composite materials in the field of high barrier properties. Detailed Implementation

[0020] Unless otherwise specified, all raw materials used in this invention are commercially available or prepared according to conventional methods in the art. Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. Other aspects of this invention will be apparent to those skilled in the art from the disclosure herein. The invention is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0021] Unless otherwise specified, experimental methods in the following examples are generally performed according to national standards. If no corresponding national standard exists, general international standards, standard conditions, or conditions recommended by the manufacturer are followed. Unless otherwise stated, all parts are parts by weight, and all percentages are weight percentages.

[0022] It should be noted that those skilled in the art can make various changes and improvements without departing from the concept of this invention. These all fall within the scope of protection of this invention.

[0023] In the following examples and comparative examples, some raw material specifications and sources are described, but not limited to these materials:

[0024] Bisphenol A type epoxy resin: grade E-20, epoxy equivalent of 450-560 g / mol, supplier is Qingdao Baichen New Material Technology Co., Ltd.

[0025] Curing agent methyl nadic anhydride: Supplier: Shandong Duoju Chemical Co., Ltd.

[0026] Curing agent methyltetrahydroanic anhydride: Supplier: Jinan Mingxin Chemical Co., Ltd.

[0027] Curing agent triethylenetetramine: Supplier: Shandong Jinhe Chemical Co., Ltd.

[0028] Accelerator 2-methylimidazole: Supplier: Zhongshan Dixin Chemical Co., Ltd.

[0029] Accelerator benzylimidazole: Supplier: Hubei Xinghengye Technology Co., Ltd.

[0030] Accelerator benzyl dimethylamine: Supplier: Wuhan Jixin Yibang Biotechnology Co., Ltd.

[0031] Fluorinated graphene, grade CF-X10; particle size D50: 1μm, 5μm, 10μm, 20μm, 50μm, Cenfu (Shanghai) Fine Chemicals Co., Ltd.

[0032] The reagents described above are only for illustrating the source and composition of the reagents used in the experiments of this invention, so as to provide full disclosure, and do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0033] Example 1:

[0034] 300 parts of curing agent methylnadic anhydride, 600 parts of bisphenol A epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0035] Example 2:

[0036] 300 parts of triethylenetetramine curing agent, 600 parts of bisphenol A type epoxy resin, 10 parts of 2-methylimidazole accelerator, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0037] Example 3:

[0038] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0039] Example 4:

[0040] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator benzylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0041] Example 5:

[0042] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator benzyl dimethylamine, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0043] Example 6:

[0044] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 5 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0045] Example 7:

[0046] Mix 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) evenly, add the mixture to a mold, and set an electric field with an electric field strength of 10 kV / m around the mold. Cure at 75℃ for 2 hours and at 165℃ for 2 hours, then open the mold to obtain the product.

[0047] Example 8:

[0048] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 20 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0049] Example 9:

[0050] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 5 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0051] Comparative Example 1:

[0052] Mix 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) evenly and add the mixture to a mold. Cure at 75℃ for 2 hours and at 165℃ for 2 hours, then open the mold to obtain the product.

[0053] Comparative Example 2:

[0054] Mix 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) evenly, add the mixture to a mold, and set an electric field with an electric field strength of 1 kV / m around the mold. Cure at 75℃ for 2 hours and at 165℃ for 2 hours, then open the mold to obtain the product.

[0055] Comparative Example 3:

[0056] Mix 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 10 μm) evenly, add the mixture to a mold, and set an electric field with an electric field strength of 20 kV / m around the mold. Cure at 75℃ for 2 hours, then at 165℃ for 2 hours, and finally open the mold to obtain the product.

[0057] Comparative Example 4:

[0058] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 50 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0059] Comparative Example 5:

[0060] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of fluorinated graphene (particle size D50 of 1 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0061] Comparative Example 6:

[0062] 300 parts of curing agent methyltetrahydroanic anhydride, 600 parts of bisphenol A type epoxy resin, 10 parts of accelerator 2-methylimidazole, and 60 parts of graphene oxide (particle size D50 of 10 μm) were mixed evenly and added to a mold. An electric field with an electric field strength of 8 kV / m was set around the mold. The mixture was cured at 75℃ for 2 hours and then at 165℃ for 2 hours. The mold was then opened to obtain the product.

[0063] The performance testing methods for the products obtained in the above embodiments and comparative examples are as follows:

[0064] Bending strength was tested according to standard ISO 178, with the test specimen size being 80mm*10mm*4mm and the test speed being 5mm / min;

[0065] Gasoline permeability coefficient: Tested according to GB / T 1038-2022 standard.

[0066] The performance test results of the products obtained in each embodiment and comparative example are shown in Table 1 below:

[0067] Table 1 Performance Test Results

[0068] Test Project Tensile strength (MPa) Transmission coefficient (23℃, 50% RH, unleaded gasoline) Example 1 109 0.023 Example 2 115 0.019 Example 3 128 0.010 Example 4 111 0.021 Example 5 103 0.028 Example 6 107 0.024 Example 7 115 0.020 Example 8 116 0.019 Example 9 108 0.023 Comparative Example 1 89 0.051 Comparative Example 2 93 0.044 Comparative Example 3 101 0.036 Comparative Example 4 95 0.041- Comparative Example 5 93 0.043- Comparative Example 6 107 0.042

[0069] As can be seen from the table above, the addition of fluorinated graphene to the epoxy resin system of this invention can significantly improve the mechanical properties and barrier properties of the composite material, greatly expanding the application of epoxy resin composite materials in the field of high barrier properties.

[0070] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. An epoxy resin composite material, characterized in that: It is prepared from the following components in parts by weight:

2. The epoxy resin composite material as described in claim 1, characterized in that, The epoxy resin is selected from at least one of glycidyl epoxy resins and non-glycidyl epoxy resins.

3. The epoxy resin composite material as described in claim 1, characterized in that, The epoxy resin is selected from at least one of tetrabromobisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic glycidyl ether resin, bisphenol S type epoxy resin, linear phenolic epoxy resin, and alicyclic epoxy resin.

4. The epoxy resin composite material as described in claim 1, characterized in that, The curing agent is selected from at least one of acid anhydride curing agents, amine curing agents, synthetic resin curing agents, and polysulfide rubber curing agents.

5. The epoxy resin composite material as described in claim 4, characterized in that, The amine curing agent is selected from at least one of polyamine curing agents, imidazole curing agents, tertiary amine curing agents, boramine and its boramine complex curing agents.

6. The epoxy resin composite material as described in claim 1, characterized in that, The curing agent is selected from at least one of isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, diethylenetriamine, triethylenetetramine, ethylenediamine, triethanolamine, m-phenylenediamine, tetraethylenepentamine, hexamethylenediamine, 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, 4,4′-diaminodiphenylmethane, and N,N′-dimethylpiperazine.

7. The epoxy resin composite material as described in claim 1, characterized in that, The curing agent is selected from at least one of benzophenone tetracarboxylic anhydride, pyromellitic anhydride, phthalic anhydride, methyltetrahydroanhydride, methylnadic anhydride, and dodecyl succinic anhydride.

8. The epoxy resin composite material as described in claim 1, characterized in that, The accelerator is selected from at least one of benzyldimethylamine, 2-methylimidazole, triethanolamine, and benzylimidazole.

9. The epoxy resin composite material as described in claim 1, characterized in that, The fluorinated graphene has a fluorine-to-carbon ratio of ≥1.0, a bulk density of ≥0.02 g / cm³, and a particle size D50 of 1-20 μm.

10. A method for preparing an epoxy resin composite material, characterized in that: Mix 250-600 parts of curing agent, 500-800 parts of epoxy resin, 1-30 parts of accelerator, and 20-130 parts of fluorinated graphene evenly, and pour the mixture into a mold. Set up an electric field around the mold with a strength of 5-10 kV / m. Cure at 70-80℃ for 1-3 hours, or at 150-190℃ for 1-12 hours. Then, open the mold to obtain the product.

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